JPS6021652B2 - automotive glass run - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a glass run for automobiles. More specifically, the present invention significantly improves abrasion resistance performance and stress resistance under special environments, such as abrasion resistance after heat resistance tests, abrasion resistance after weather resistance tests, and abrasion resistance in high-temperature atmospheres. This invention relates to an improved glass run for automobiles. Glass runs for automobiles are required to have various performances under harsh conditions in special atmospheres, including heat resistance and weather resistance under high loads. In general, glass runs that pass through automobile windows require a glass holder made of a material with low frictional resistance when supporting the window glass and window frame, especially when the glass can be slidably opened and closed. . In automobiles, the window frame, that is, a weather strip made of rubber or resin, is used to fix the window glass and the window frame.In the areas where the glass slides, paint is applied to the areas where the sliding glass contacts the sliding glass. Glass run coated with is used. Conventional glass run products for automobiles are particularly poor in abrasion resistance after heat aging, abrasion resistance after tear resistance tests, and abrasion resistance in high-temperature atmospheres, and also suffer from sliding of the glass and glass run during vertical movement of the glass. Their resistance values are high, and improving their performance has been a challenge in this technical field. When examining the condition of automotive glass run through abrasion resistance tests, it is found that the coating itself may wear out, the coating itself may crack, and in some cases, the coating may peel off from the base material at the interface. As a result of these studies, the present inventors found that in automotive glass runs, the paint applied to the base material is the biggest factor in determining the wear resistance and sliding resistance of the base material. By improving the abrasion resistance, we succeeded in significantly improving the performance of automotive glass runs. In other words, the paints conventionally used for glass run include polyacrylic acid ester, polyvinyl acetate, epoxy, polyvinyl acetal, and vinyl chloride paints; The abrasion resistance after the film resistance test and the abrasion resistance in a high temperature atmosphere are poor, and at the same time, the sliding resistance between the glass and the glass run due to the vertical movement of the window frame glass is high. As a result of repeated research on the above-mentioned problems, the present inventors have developed a method using polyvinyl chloride resin as a base material, and the spiders described below.
'B}, {C}, By applying a paint prepared from blood components, we can eliminate the above-mentioned drawbacks of conventional products and provide a glass run for automobiles that has excellent workability during manufacturing. It's arrived. Hereinafter, the automotive glass run according to the present invention will be described in detail. The glass run for automobiles of the present invention uses polyvinyl chloride resin as a base material, and after the surface of the base material is treated as desired, the paint described in detail below is applied thereto, and the glass run is heated from room temperature to 180 oo
The coating composition used in the present invention cures at a temperature in the range of 1% by weight based on total weight
A hydroxyl group at the end obtained by reacting a polyester having a hydroxyl group at the end synthesized from the following low-molecular trifunctional polyol and a diisocyanate at a molar ratio of NC○:OH=0.6 to 0.95:1. A urethane prepolymer having a urethane prepolymer having an isocyanate group at the end obtained by reacting a low-molecular trifunctional polyol and a diisocyanate at a molar ratio of NCO to OH of 3:1. Urethane prepolymer 1-15 parts by weight, metal soap 2-1
The coating composition is prepared by dissolving 5 to 20 parts by weight of silicone oil in an organic solvent. In the above urethane prepolymer A, if the polyester polyol having hydroxyl groups has 2 or more moles of OH groups per 1 mole of COO, the paint film will be hard and brittle, resulting in poor wear resistance. becomes worse. Further, if the OH group is 1.04 mole or less per 1 mole of COO, the paint film will have poor abrasion resistance in a high-temperature atmosphere, and at the same time the product will have a high hyperdynamic resistance value. For example, in a product like this one, it becomes impossible to open and close the glass after the glass has been moved up and down several thousand times. In urethane prepolymer A, NC per mole of OH group
Urethane Brevo 0 Limer obtained by reacting with a molar ratio of O groups of 0.6 mol or less or 0.95 mol or less also has high sliding resistance, and also has good wear resistance in high-temperature atmospheres. bad. The above-mentioned C3 to C6 saturated low molecular weight diols include propylene glycol, butylene glycol, bentanediol, hexanediol, etc.
Examples of 4-C6 saturated organic dicarboxylic acids include adipic acid and succinic acid, and examples of low-molecular trifunctional polyols include glycerin and trimethylolpropane. The diisocyanate includes 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, and the like. The metal soaps used in the present invention include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, calcium laurate, strontium stearate, barium stearate, barium laurate,
Examples include barium 2-ethylhexoate, barium ricinoleate, zinc stearate, zinc laurate, cadmium stearate, cadmium laurate, and lead stearate. Further, examples of the silicone oil include dimethyl silicone oil, methyl chloride silicone oil, and the like. These silicone oils can preferably have a viscosity of 1 to 200,000 Cst. For the above-mentioned coating composition used in the present invention, {B' component, 1 to 15 parts by weight, preferably 1 to 15 parts by weight of the wind component, preferably 1 to 15 parts by weight of the wind component.
0 parts by weight

Component [B} is used in a proportion of 4 to 6 parts by weight. ■If component [B} exceeds 15 parts by weight relative to 10 parts by weight, the resulting coating film will be extremely hard and brittle, and its adhesion to the PVC resin base material will be extremely poor. . For example, in the case of such products, the paint flakes off just by repeating the vertical movement of the glass several dozen times.
The swamp resistance value increases rapidly, making it difficult to open and close the window glass, and at the same time, the abrasion resistance becomes extremely poor. Also ■Ingredient 10
Component (B) is 1 part by weight or less with respect to parts by weight of
The resulting coating film is sticky, and in glass runs made with such coatings, the glass and coating film adhere to each other, making it impossible for the glass to move up and down. Furthermore, the wear resistance in a high temperature atmosphere is also very poor. The proportion of the metal soap used is 2 to 10 parts by weight per 10 parts by weight of the wind component.
Preferably it is 8 to 5 parts by weight. (2) When the amount of metal soap is less than 2 parts by weight based on the weight of component 10, the abrasion resistance is very poor, and when the sliding resistance of a glass run manufactured using a paint having this composition is measured, it shows a significantly high value. In addition, if metal soap is used in a ratio exceeding 10 parts by weight to 10 parts by weight of component (1), the metal soap will be exposed on the surface of the product, which will not only cause a very poor appearance but also extremely poor wear resistance. descend. If the proportion of silicone oil is less than 5 parts by weight, the abrasion resistance of the product after weathering will be poor. Further, if the amount is 200 parts by weight or more, the stability of the solution will deteriorate. When preparing the above-mentioned urethane prepolymer, catalysts such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, etc., which generally promote the urethanization reaction, may be used as necessary. Further, carbon black may be added if necessary.
The coating method used for manufacturing the automotive glass run of the present invention includes dip coating, spray coating,
Brush coating, knife coating, roll coating, etc. are exemplified, but are not specific. Various organic solvents are used to make the above-mentioned components into a coating composition, but in contrast to the mixture of the urethane polymer component () and the urethane prepolymer component (B), a mixture of a good solvent and a poor solvent is used. , good solvent/poor solvent = 2/
It is preferable to use it at a ratio of 1 to 10/1 (weight ratio). Examples of good solvents for the mixture of the urethane prepolymer (2) and the urethane prepolymer 'B' include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexane, dioxane, dimethyl sulfoxide, Examples of poor solvents include aromatic solvents such as benzene, toluene, xylene, carbon tetrachloride, chloroform, tricloethylene, 1,1,
Examples include halogen-containing solvents such as 1-trichloroethane and 1,1,2-trichloroethane, ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, and ether solvents such as ethyl ether and hexyl acetate. In this case, if a good solvent alone or a good solvent/poor solvent = 10/I (weight ratio) or more is used for a mixture of the urethane prepolymer of wind and the urethane prepolymer of (B}, The urethane prepolymer and silicone oil are completely separated, and in glass run manufactured using this system, the silicone oil is completely separated from the urethane paint.In other words, in this case, the urethane prepolymer and {B } Dissolve only the urethane prepolymer in a solvent, apply it to the PVC resin base layer, harden it, and the result is the same as that of applying silicone oil, and the film resistance and abrasion resistance are also very low. In addition, if a poor solvent is used alone or in a ratio of good solvent/costly solvent = 2/1 (weight ratio) or less for the urethane prepolymer of 'B', the urethane prepolymer of 'B' will become crystallized. Because it precipitates as
It does not adhere uniformly to the PVC base material, and its adhesion to the PVC base material is very poor, resulting in extremely poor abrasion resistance.
The mixing ratio of good solvent and poor solvent is good solvent/poor solvent = 2/1 ~
A ratio of 10/1 (weight ratio) shows the best wear resistance. When used in the range of good solvent/poor solvent = 2'1 to 10/1 (weight ratio), 0 means that the urethane prepolymer mixture and silicone oil of ■,'8} are completely separated; It is not uniform and some parts are made of urethane prepolymer.
and a part of it is compatible with the urethane prepolymer, so in glass run manufactured using this mixture as a paint, part of the silicone oil is on the paint surface, and part of the silicone oil is on the surface of the paint. This means that the same amount is also present in the urethane paint. As a result, even after the weather resistance test, the silicone oil on the paint surface simply disappears, and since the silicone oil is still present in the urethane paint, the wear resistance is very good, and the swamp movement after the weather resistance test is The resistance is also very good. If the silicone oil is completely dispersed in the paint, the adhesion between the paint and the PVC base material will deteriorate, resulting in extremely poor sliding resistance and abrasion resistance. The characteristic advantage of the glass run for automobiles of the present invention is that it can be left at room temperature for several hours or heated for several minutes at a temperature of 180°C or less, resulting in low sliding resistance and wear resistance on the PVC base material surface. It is possible to form an excellent paint film. Here, room temperature refers to the indoor temperature that can be obtained in normal climate without using heating means such as a dryer or heating furnace. A method of curing at room temperature is preferred because it does not require a heating device and is easy to work with, but if there is a requirement such as large-scale processing, it is also possible to use heating means.
The temperature during the heat treatment is 180°C or less. 180qo
Temperatures above this level are undesirable because there is a concern that Motomura will deteriorate.
Preferably, the heat treatment is performed at a temperature of 100 oo or less. Any suitable means may be adopted as the above-mentioned heating means. The present invention will be explained below with reference to Examples. All parts in the examples are by weight. The PVC base material and the weight 3 material (urethane prepolymer) used in the examples were prepared as follows. [PVC Motomura polyvinyl chloride] 0 parts by weight, dioctyl phthalate 9
A mixture of 0 parts by weight of barium dilaurate, 1.5 parts by weight of barium dilaurate, 2 parts by weight of zinc laurate, and 1 part by weight of dibutyltindimalate was extruded from a press at 150 to 170 qo to produce a base material. {0) Weight A 10 parts by weight of 1,4-butanediol, 14 parts by weight of 1,6-4 hexanediol. 2 parts by weight of trimethylolpropane, 163 parts by weight of adipic acid. Using parts by weight of insects, 150
L polyester was synthesized by reacting with oo for 1 feeding time. 100 parts by weight of the obtained polyester, 8 parts by weight of 4,4'-diphenylmethane diisocyanate, 15 parts by weight of cyclohexanone, and 5 parts by weight of ethyl acetate were reacted at 80°C for 3 hours in dry nitrogen gas. A urethane polymer was produced. Polymer B Using 10 parts by weight of trimethylolpropane, 553 parts by weight of 4,4'-diphenylmethane diisocyanate, and 480 parts by weight of butyl acetate, 3 parts by weight at 80°C in dry nitrogen gas.
A urethane prepolymer was synthesized by a time reaction. Example 1 A coating material was prepared by mixing parts of heavy AIOO, 25 parts of dimethyl silicone oil (viscosity approximately 10 Cst), 15 parts of zinc stearate, parts of heavy BI, and 3 parts of carbon black. The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Example 2 A coating material was prepared by mixing a heavy AIOO part, 25 parts of dimethyl silicone oil (viscosity: about 100,000 Cst), 15 parts of lead stearate, a polymer BIO part, and 3 parts of carbon black. The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Example 3 Part of heavy AIOO, 25 parts of dimethyl silicone oil (viscosity approximately 10 Cst), 15 parts of aluminum stearate
1 part, heavy BIO part, and 3 parts of carbon black,
A paint was prepared. The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Example 4 A coating material was prepared by mixing parts of heavy AIOO, 25 parts of dimethyl silicone oil (viscosity: about 100,000 Cst), 15 parts of zinc laurate, parts of heavy BIO, and 3 parts of carbon black. The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Example 5 A coating material was prepared by mixing parts of heavy material AIOO, 25 parts of dimethyl silicone oil (viscosity approximately 100,000 Cst), 15 parts of calcium stearate, part of heavy material BI, and 3 parts of carbon black. The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Example 6 Part of heavy AIOO, 25 parts of dimethyl silicone oil (viscosity approximately 100,000 Cst), 15 parts of barium stearate,
A paint was prepared by mixing heavy weight BI and 3 parts of carbon black. The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Control example 1 Dimethyl silicone oil (viscosity approximately 100,000 Cst) 10
Anchor part, 3 parts of carbon black and 10 parts of toluene were mixed, and this was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Control Example 2 A coating material was prepared by mixing parts of heavy material AIOO, 25 parts of dimethyl silicone oil (viscosity: approximately 100,000 Cst), parts of heavy material BI, and 3 parts of carbon black. The resulting paint was applied to a PVC base material and dried at room temperature to produce a glass run for automobiles. Control Example 3 Parts of heavy AIOO, 15 parts of cadmium stearate, 3 parts of heavy BI Akatsuki, and 3 parts of carbon black were mixed to prepare a paint. The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Control Example 4 A urethane paint was prepared by mixing heavy AIO Ikarito, heavy BI Ikaribe, and 3 parts of carbon black. The obtained paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Control example 5 100 parts of polyester obtained in the middle of heavy material A, 4,
Using 8 parts of 4-diphenylmethane diisocyanate and 20 parts of trichlorethylene, 8,000 g of
The mixture was reacted for 3 hours to produce urethane prepolymer F. The obtained urethane prepolymer FIO anchor, 25 parts of dimethyl silicone oil (viscosity of about 100,000 Cst), 15 parts of zinc stearate, part of heavy weight BIO, and 3 parts of carbon black were mixed to prepare a paint. The obtained paint is made into PVC
It was coated on a substrate and dried at room temperature to produce a glass run for automobiles. Control Example 6 10 parts of polyester obtained during the production of heavy material A, 8 parts of 4,4'-diphenylmethane diisocyanate,
Using dimethylformamide 20 base, react in dry nitrogen gas at 8 pm for 3 hours to form urethane polymer G.
was manufactured. A paint was prepared by mixing the obtained urethane prepolymer GIOO part, 25 parts of dimethyl silicone oil (viscosity: about 100,000 Cst), 15 parts of zinc stearate, heavy weight BI base part, and 3 parts of carbon black. The resulting paint was applied to a PVC substrate and dried at room temperature to produce a glass run for automobiles. Using the automotive glass runs obtained in Examples and Control Examples, sliding resistance measurements and abrasion resistance tests were conducted under the following conditions. The test results are shown in the table. ■ Sliding resistance was measured using TENS ratio ON/UTM-1/5000 manufactured by Toyo Saiki Co., Ltd.
Using 1 W, glass (5 layers thick) was roughly attached to the glass run, a load of 3k9 was applied to the glass, the glass run was pulled (pulling speed 20 mm/min), and the resistance value at that time was measured. ■ The abrasion resistance test was conducted as follows. Testing machine: KI type abrasion testing machine Test conditions: Abrasion element Glass (thickness 5 side) Load
3k9 wear child cycle
60 times/min 0 Friction element stroke
145 side test method A sample is attached to the above testing machine and the painted surface is abraded under the above conditions. {1} Abrasion resistance test after heat resistance test The sample was placed in an incubator at 80°C and left for 200 hours, and then abrasion was performed at room temperature. ■ Abrasion resistance test after inertia test After being exposed to a Sunshine Weather-Ometer using two carbon arc lamps for 20 hours, abrasion tests were performed at room temperature. Leg Abrasion resistance test in high temperature atmosphere The sample is worn in 60oo atmosphere. Table x The operating load on the handle increased to over 8Kta, making it impossible to move the glass up and down.

Claims (1)

[Claims] 1. A glass run for automobiles made of a polyvinyl chloride resin base material, on the surface of which (A) saturated low molecular weight diols of C_3 to C_6, organic dicarboxylic acids of C_4 to C_6, and this saturated low molecular weight diol. A polyester having a hydroxyl group at the terminal synthesized from a low-molecular trifunctional polyol of 1% by weight or less based on the total weight of the organic dicarboxylic acid and a diisocyanate are combined with NCO:OH=0.6 to 0.
．． A urethane prepolymer having a hydroxyl group at the end obtained by reacting at a molar ratio of 95:1, a low-molecular trifunctional polyol (B) and a diisocyanate are combined with 100 parts by weight of this urethane prepolymer (A) in NCO:OH.
= 1 to 150 parts by weight of a urethane prepolymer having an isocyanate group at the end obtained by reacting at a molar ratio of 3:1, (C) 2 to 100 parts by weight of metal soap, (D) 5 to 200 parts by weight of silicone oil, and 5 to 200 parts by weight of silicone oil. An automotive glass run characterized by being coated with a coating composition dissolved in a solvent and cured.